DD157302A5 - INSECTICIDES AND NEMATOCIDE COMPOSITION - Google Patents

Abstract

The invention relates to compositions for the control of insects and nematodes. The object of the invention is to provide such broad insecticidal compositions which are also useful for controlling the corn rootworm and the southern armywoorm. According to the invention, in the novel compositions, compounds of the general formula wherein R is alkyl of 1 to 8 carbon atoms, R 1 is phenyl, or substituted phenyl of 1 to 4 substituents, wherein the substituents have been selected from the group consisting of alkyl with 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, chlorine, bromine, fluorine, nitro and trifluoromethyl, and R deep 2 tertiary alkyl with 4 represents up to 8 carbon atoms.

Description

Insects and wematodes

The invention relates to a composition for controlling insects and uematodes containing O-aryl-S-tertiary alkyl-alkylphosphondithioate compounds, a process for the preparation of these compounds and a process for controlling insects and nematodes using these compounds. «

Chara kteristik the known t echni rule Solutions

Some insecticides based on O-arylphosphonedithioates are known from US Pat. No. 3,209,020. None of the compounds described in this US patent corresponds to those of the abovementioned compounds in which a tertiary alkyl group is present «

Aim of the invention .

It is an object of the invention to provide novel insecticidal and ultraviolet active insect control compositions which are also useful in the control of the corn rootworm and the southern armywoorm.

Presentation of the _" invention" of the invention

The invention has for its object to find new compounds with the desired properties, which are suitable as an active ingredient in compositions for controlling insects and ÜTematoden.

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According tingsgemäß in the new compositions for controlling insects and uematodes as Wirkstoff.'eine compound of the general formula

; R - PQ '

SR ₂ :.

applied,.

wherein R is alkyl of 1 to 8 carbon atoms, R is phenyl or substituted phenyl of 1 to 4 substituents, said substituents being selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, chlorine, bromine, fluorine, nitro and trifluoromethyl, and R _? Tertiary alkyl having 4 to 8 carbon atoms

The invention also relates to a process for the preparation of a compound of the general formula

wherein R is alkyl with. From 1 to 8 carbon atoms; R is phenyl or 'substituted phenyl having 1 to 4 substituents selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylsulfinyl having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms and

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atoms, chlorine, bromine, fluorine, hi tr ο and tri fluorine thy 1 existing group; and R ₂ denotes tertiary alkyl having 4 to 8 carbon atoms »

· F. , , -

The process consists in a reaction of an S-Tertiäralkylalkylphosphondithiohalogenids of the general formula

R - PCT

'SR ₀

wherein R and R _{2 have} the abovementioned meaning and X is halogen, with a phenol or substituted phenol of the general formula.

wherein Y is alkyl of 1 to 4 carbon atoms} C ₁ -C * alkoxy, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, chlorine, bromine; Fluorine, litro ttad tri fluorine thy 1 <£ * • bes-tefeeiid-eir ^ rupp-® and η = 1 to 4 means in the presence of a base.

The compounds of the invention have a broad range of insecticidal activity and are of particular interest in the control of the corn rootworm and the southern armywoorm because of their stability and long residual activity.

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An essential structural feature of the compounds of this invention is that Ro in the above formula is tertiary alkyl.

ι ··

It has been found that the branched compounds of the present invention have high toxicity to Southern Army Worm. They are also characterized by a long residual activity against the cereal rootworm.

The compounds of the present invention can be prepared by methods described in U.S. Patent No. 3,209,020. Preferably, the compounds of the present invention are prepared from a starting material which is an S-alkyl-alkylphosphondithiohalide, the preparation of which is illustrated in Example 1. The S-alkyl-alkylphosphondithiohalide is reacted with a phenol or substituted phenol in the presence of a base to give the compounds of the present invention. »

The preferred reaction sequence is as follows:

Base _e HCl

Where R is alkyl of 1 to 8 carbon atoms.

R ₁ aryl, Rp tertiary alkyl of 4 to 8 carbon atoms

and X is halogen, preferably Clrlor.

Suitable aryl groups are phenyl and phenyl, mono-, di-, tri "or tetrasubstituted with alkyl 'having 1 to 4 carbon atoms, C ₁ -C 4 -alkoxy, alkylthio having 1 to 4 carbon atoms

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atoms, alkylsulfinyl having 1 to 4 carbon atoms, alkylsulfonyl having 1 to 4 carbon atoms, chlorine, bromine, fluorine, nitro or trifluoromethyl, or combinations of the groups mentioned. · _;

The reaction is advantageously carried out at a temperature of 0 to 100 ⁰ C in an organic solvent in the presence 'of a tertiary amine or a wäßrigen.Base such as aqueous ITaOH. ^:

Suitable organic solvents are, for example, benzene, toluene, cyclohexane and 2-butanone or acetone.

Suitable tertiary amines are trimethylamine, triethylamine, dimethylaniline, diethylaniline and pyridine. The alkylphosphondithioate compounds of the present invention are effective as insecticides and / or nematocides at low concentrations. Since only small amounts of the compounds are to be used for effective control, it is generally not advisable to use the compounds as such. The compounds are therefore preferably used as liquid compositions or in combination with other excipients The compounds of the present invention may be present as dispersions or emulsions as an effective component Since the active compounds are substantially water-insoluble, a small amount of an inert, non-phytotoxic organic solvent should be added which can be easily dispersed in an aqueous medium For example, an effective liquid composition can be prepared with the active component, acetone or ethanol, water

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5B 6Ο9Ί2

and a surfactant such as Tween-20 (polyoxyethylene sorbitan monolaurate) or any other known surfactant.

ί.

The compositions with the active compounds may also be present as dust or granules. Thus, for example, the active compound may be mixed with a suitable solid carrier such as kaolinite, bentonite or talc in amounts of from 5% to 20% by weight.

For insect control, the active ingredients are used at concentrations of from 0.01% to about 1% by weight of the total formulation. As üematozid the active compound is effective in the range of 0.56 to 5> 6O kg / ha (0.5 to 5 pounds / acre) *

Under ideal conditions, depending on the pest to be controlled, the low application rate provides adequate protection. On the other hand, unfavorable weather conditions, resistance of the pest and other factors may cause the active ingredient to be used in higher proportions «

In the case of a soil-borne pest, the formulation containing the active compound is evenly distributed over the area to be treated in a conventional manner. The active compound may be flushed into the soil or left over by water spraying over the area or the natural history (rain). After application, the formulation can be distributed in the soil by plowing or drilling or harrowing. They may be applied before planting, after planting but _s hatj before used the germination or after · germs.

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Execution at s pi e 1

The following examples serve to illustrate the present invention:.

Example 11

Preparation of S-tert-butyl-ethylphosphondithiochloride (intermediate) ' ^: .

To a solution of 80 g (0.5 mol) of ethylphosphonothiodichloride in 500 ml of dry toluene was added 50 g (0.55 mol) of 2-methyl-2-

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Propanethiol given «, · The. Solution was stirred with dropwise addition of 60 g (0.6 mol) of triethylamine. After complete addition of the amine, the mixture was stirred, heated to 80 ° C for 3 hours and allowed to stand overnight. The reaction mixture was washed first with 5% cold HCl solution (100 ml), then with 5% cold NaOH solution (100 ml) and further twice with 100 ml of water each time. When dried over magnesium sulfate, the toluene was evaporated under a water-jet vacuum and the oily residue was distilled at 78-80 ° C./0.2 mm. The yield was 60 g (55.4 % of theory). The structure was confirmed by the NMR spectrum.

Example 2

CH.

To a solution of 10 g (0.046 mol) of S-tert-butyl-ethylphosphondithiochlorid in 15 ml of acetone was added 6.5 g (0.05 mol) of 4-chlorophenol followed by 6.0 g (0.06 mol) of triethylamine , The mixture was stirred at room temperature overnight and then heated to 50 ° C for one hour. The solution was diluted with toluene, filtered off from the amine hydrochloride salt and extracted with water, 5% NaOH solution and again with water. The organic phase was dried over anhydrous sodium sulfate and then the solvent stripped under vacuum. The remaining liquid was subjected to a high vacuum (0.05 mm) for one hour at 90-100 ° C to determine any unreacted

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Phosphondithiochlorid to evaporate. The resulting clear liquid with a mass of 13.5 g (87.7% yield) is a pure product of the title compound, which was confirmed by the fflR spectrum. ,

NME (CDCl ₃ ) cf 1.4 (3H, ä of t, Jp ^ gO Hz, J _n = 5Hz); 1.5 (9H, s); 2.4 (2H, m); 7.25 (4H, s) Examples 3 to 16 "

In an analogous manner as in Example 2, the compounds listed in Table 1 were prepared.

Example 17

Experiments with regard to cereal rootworm intrinsic activity, crop phytotoxicity and activity against the Southern armyworm

A. Cereal Rootworm Intrinsic Activity (CBW)

The test compound was added in a 1% solution with acetone or ethanol. The stock solution was then diluted to an appropriate concentration with an aqueous solution of Tween 20 and water (e.g., 100, 10, 1, .O, 1 /, 0.05 ppm). Two ml of this solution was then pipetted into a 9 cm Petri dish containing about two layers of filter paper. 2nd instar larvae were placed in the dish and the dish was covered. After the larvae were exposed to this environment for 2 days (48 hours), the killed and dying larvae were detected. The insecticidal activity is primarily due to direct contact and exposure to the vapors with minimal ingestion. The results are shown in Table 2.

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AQ

B, Southern Army Worm - Own Activity (SAY /) '

The stock solution (1 % ) of the test material was prepared with acetone and diluted to the desired concentration with a 500 ppm Tween 20 aqueous solution.Limebeans leaves were briefly dipped in the solution and placed in Petri dishes (100.times.15 mm), containing two filter papers moistened with 2 ml of water Each Petri dish contained one leaf and was left open to let the solution dry on the leaf Five larvae in the third stage (instar) of the Southern Army worm (Spodoptera eridania The insects were held at 25 ° C (78 ° F) for 72 hours and the G-rad of mortification recorded The results are the average of two experiments.

table

SE

example

CH,

, .CH.

C ₂

7 CH ₃ 8th ^C 2 ^H 5 9 OH, 10 O ₂ H ₅ 11 O ₂ H

phenyl

phenyl ·

2-methylthylphenyl

2-Me thyphenyl

4-Methyl-phenyl

4-methylphenyl

4 (methylthio) phenyl 4 (methylthio) phenyl

3-methyl-4- (methylthio) phenyl

tert -butyl

tert- butyl tert- butyl

tert- butyl

tert. Butyl tert- butyl

tert-butyl tert -butyl

tert. butyl

MR (C) DCl ₃ )

1, 55C9H, s); 2.35 (3H, a, Jp = 7.3C5H _? S)

1.4 (3H, d of t, Jp = 20Hz, ^ _τ = 5Ηζ), 1.5C9H, s), 2.4C2H, m), 7.3 (3H, s)

1.55 (9H.s); 2.25 (3H, s); 2.35 (3H, d, Jp = 14Hz); 7.4 (4H, m)

1.4 (3H, d of t, Jp = 20Hz, J _w «5Hz) :. 1.55 (9H ₉ S); 2 ₇ 3 (3H, s); 2> t (2H, m); 7.4 (4H _? M). ,

 1.55 (9H, sJ; 2, -35 (3H, d, jp = i4Hz); 2.38 (3H, s.5; 7.3 (4H., S)

1j4 (3H, d of t, Jp = 20Hz, J _TT = 5Hz); · 1.5C9H, s); 2.35 (3H, s); 2.4 (2H, m); 7.25 (4H, s).

1.55 (9H, s); 2.3 (3H, d, Jp = l4Hz); 24 (3H) 73 (4H)

1.4 (3H, d of t, Jp = 20Hz, J _w = 5Hz); 1.55-9H, s); 2.4 (2H »; -2, fe (3H, s) 7.35C4H, s)

1.4 (3H, d of t, Jp = 20Hz, J _TT = 5Hz); 1,5C9H, .s); 2.3 (3H, s): 2.4 (2H, m) ;. 2,4 (3H, s); 7,2 (3H, s)

Table 1 (Port setting

Example 12

CH,

4rChiorophenyl

, 2-Flüorophenyl

J ₃ H ₅ 2-methyl-4-chlorophenyl

4-Witrophenyl

tert- butyl

CgH, - 4-fluorophenyl tert. butyl

tert -butyl

tert -butyl

tert-butyl MR (CDCl ₃₎ "1.5 (9H, S ^, 2.3 (3H, d, Jp = UHZ);

1 _? 4 (3H d of t, Jp = 20Hz *, J _w = _5.Hz?): 1.5 (9H, s), 2.4 (2H, m), 7.25 (4H, m;

1, -4 (3H, d of t, Jp = 2OHz, J _M = 5Hz); •. 1.55 (9H, s); 2,4C2H, m); 7V-4 (4H, m)

1.4 (3H, d of t, Jp = 20Hz, J _w = 5Hz); 1.55 (9H, s); 2.25 (3H, s); 2.3 (2H, m); 7.4 (3H, m)

1.4 (3H, d of t, Jp = 2OHz, J _n = 5 Hz); 1.5 (9Η ₅ 5); 2 _? 4 (2Η _{? Κ} ); 7 _? 95 ( ^Μ 4Η ^)

Note: All spectra were measured on a Varian BM 360, a 60 Mz instrument using CDCl ,, as solvent. All chemical shifts are contained in ΰ with (CEL). Si as an internal standard.

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Table 2 '

connection 500 SAW. CRW Effort 1 100 0.1 from example 100 Amount (ppm) 95 100 100 100 100 100 70 2 100 100 70 50th 3 90 65   - 4 90 75 - - 5th 100 40   -; 30 6 100 95 - 12 100 100 13 , 100 100 - ^'14 100 95 ¹ 5 90 16

Claims (1)

invention claim 1 «Insecticidal and nematocidal composition, characterized in that it contains as active ingredient a compound of the general formula in an amount effective as an insecticide or uematocide, in addition to an inert, non-phytotoxic organic solvent or a solid carrier, wherein in the formula R, alkyl of 1 to 8 carbon atoms represents R, phenyl or substituted phenyl of 1 to 4 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, chlorine, bromine, fluorine, eftro, and trifluoromethyl Group; and R _{2 are} tertiary alkyl of 4 to 8 carbon atoms « 2 * Composition according to item 1 _$ characterized by the fact that R. Phenyl represents » 3 * Composition according to item 1, characterized in that R. represents methylphenyl. 4 »Composition according to item 1, characterized in that R. represents chlorophenyl · 5 "Composition according to any one of items 1 to 4", characterized in that R represents methyl or ethyl. 58 609 12 • AP A 01 K / 226 2 26 7 76 AS Composition according to any one of items 1 to 5, characterized in that R ₂ 'represents tert-butyl. Method for controlling insects and nematodes, characterized in that a pesticidally effective amount of a compound of the general formula is applied to these or their forms R -> ^SR 2 ' is allowed to act, wherein R is alkyl having 1 to 8 carbon atoms; R _{1 is} phenyl or substituted phenyl having 1 to 4 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, Chlorine, bromine, fluorine, nitro and üiriflttormethyl existing group; and R _{2 is} tertiary alkyl having 4 to 8 carbon atoms, 8 · Method according to item 7 for the control of G-roots of radicles, characterized in that a pesticidally effective amount of the compound of the general formula , f R - P ^ ^SR 2 ' to act on the soil, wherein R is alkyl of 1 to 8 carbon atoms; R | Phenyl or substituted phenyl having 1 to 4 substituents selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbons 58 609 12 AP A 01'Ν / 226 776 atoms, alkylsulfinyl of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, chlorine, bromine fluorine, mtrol and trifluoromethyl; and Rp is tertiary alkyl of 4 to 8 carbon atoms.